ISSN:
0009-2940
Keywords:
(Vinylidene)iridium(I) complexes
;
Iridium(III), dihydrido complexes
;
Isomerization, fac-mer
;
Iridium(III), (phenylethynyl) complexes
;
CO abstraction
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Vinylidene Transition-Metal Complexes, XVII. - Synthesis of trans-[IrCl(=C=CH2)(PR3)2] (PR3 = PMetBu2, PPh3), [IrHCl(C≡CPh)(PMe2tBu)3], and of some Dihydridoiridium(III) Complexes[IrCl(C8H14)2]2 (1) reacts with PMetBu2 in the presence of H2 to give [IrH2Cl(PMetBu2)2] (2). Treatment of 2 with acetylene yields the vinylidene complex trans-[IrCl(=C=CH2)-(PMetBu2)2] (3). The reaction of 1 with PMePh2 or PMe2tBu in the presence of H2 leads to the formation of fac-[IrH2Cl(PR3)3] (4a, 5a), which on warming to 60°C rearrange to give the more stable mer isomers 4b, 5b. Treatment of 1 with PMePh2 or PMe2tBu and phenylacetylene affords the hydrido(phenyl-ethynyl)iridium(III) compounds mer-[IrHCl(C≡CPh)(PR3)3] (8, 9), which could not be converted by phosphine elimination to the corresponding (phenylvinylidene)iridium complexes. The synthesis of trans-[IrCl(=C=CH2)(PPh3)2] (11) has been achieved by CO abstraction from [IrHCl(C≡CH)(CO)(PPh3)2] (13) by using trimethylamine oxide.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240912
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